AppendixPrincipal Characterization Techniquesof Nanostructured Macromolecules

Many experimental techniques for the characterization of bulk macromolecules areknown and widely used, but a few techniques with sufficient lateral resolutionare available to characterize nanostructured macromolecules. Among microscopytechniques, the most popular characterization methods for polymeric nanostruc-tures are Atomic Force Microscopy (AFM) and Scanning Electron Microscopy(SEM), together with Near-Field Optical Microscopy (SNOM), Scanning TunnelingMicroscopy (STM) and Transmission Electron Microscopy (TEM). Other spec-troscopic techniques that offer chemical information with sub-100 nm lateral res-olution are Infrared Reflection Absorption Spectroscopy (IRRAS) and RAMANbased techniques, i.e. micro RAMAN (μRAMAN) and Surface Enhanced RamanSpectroscopy (SERS). Dynamic Light Scattering (DLS) is also a well suited methodfor the assessment of the size of nanoparticles.

A short overview on these techniques is outlined here with some literature hints.

Atomic Force Microscopy (AFM)

A key feature of AFM is its ability to provide topographic and height maps of “soft”,organic surfaces, with nanometer lateral resolution and without causing damage[1, 2]. In general, AFM provides imaging capability in gaseous and liquid envi-ronment and is based on the use of a proper tip that acts as a mechanical probe onthe surface. AFM was invented in 1985 by Binnig, Quate, and Gerber and one of itsadvantages is to overcame the need of using conducting or semiconducting surfaces,opening to almost any type of surfaces, including polymers and biological samples.Schematically, AFM consists of a tip on a cantilever contacted to the surface with theinteratomic van der Waals forces that provides the interaction mechanism with thesample. AFM tips are usually microfabricated from Si or Si3N4, with tip radius ofabout tens of nm. The forces between the tip and sample are calculated by measuringthe deflection of the lever, by applying the Hook’s law. AFM modes of operation canbe modified for specific application requirements, ranging for example from contactmode (where the tip is in hard contact with the surface and is raster-scanned acrossthe surface being deflected), to non contact mode (where tip is quite close to the

261M.V. Russo (ed.), Advances in Macromolecules, DOI 10.1007/978-90-481-3192-1,C© Springer Science+Business Media B.V. 2010

262 Appendix:Principal Characterization Techniques of Nanostructured Macromolecules

sample, but not touching it), or using lateral forces (measuring frictional forces on asurface) or tapping mode (intermittent-contact).

Scanning Electron Microscopy (SEM)

The scanning electron microscopy is based on a high-energy beam of electrons thatscans a sample surface; the interaction between the electrons with the atoms at ornear the surface produces signals that contain information on topography, composi-tion and properties of the sample’s surface [3]. In the most common detection modei.e. secondary electron imaging, this microscopy allows to gain very high-resolutionimages revealing details of about 1–5 nm in size. In general, a wide range of mag-nifications is achievable (from about × 25 to × 250,000). Back-scattered electrons,reflected from the sample by elastic scattering can be used in analytical applicationsby using the spectra made from the characteristic x-rays emitted when the electronbeam removes an inner shell electron from the sample, causing a higher energy elec-tron to fill the shell and release energy. These characteristic x-rays can be used toidentify the composition of the sample.

Near-Field Optical Microscopy (SNOM)

SNOM microscopy can image polymeric surfaces below the diffraction limit withhigh spatial, spectral and temporal resolving power [4, 5]. This technique is particu-larly suitable for nanostructure investigation and it is based upon the passage into asmall orifice of intense and nearly planar light behind an opaque and thin metal film.A scanning tip, a detector, a focused laser light source and a piezoelectric substrateare primary components of the SNOM. By placing the detector very close (<< λ) tothe specimen surface, lateral resolution of 20 nm and vertical resolution of 2–5 nmcan be achieved.

Scanning Tunneling Microscopy (STM)

STM is a powerful microscopy for viewing surfaces at the atomic level, firstly devel-oped by Binning and Rohrer in 1981. It is based on the probe of the density of statesof a material using tunneling currents. Lateral resolution of about 0.1 nm and depthresolution of 0.01 nm can be obtained. The concept of quantum tunneling is at thebasis of STM microscopy, i.e. when a conducting tip is brought very close to ametallic or semiconducting surface, a bias between the tip and the surface allowsthe electrons to tunnel through. The variations of current as the probe crosses thesurface are translated into an image [6].

Appendix:Principal Characterization Techniques of Nanostructured Macromolecules 263

Transmission Electron Microscopy (TEM)

Transmission electron microscopy is a technique based on an electron beam, trans-mitted through an ultra thin specimen, that interacts with the sample as it passesthrough [7]. The interaction of the electrons transmitted through the specimen pro-duces an image with a significantly higher resolution than optical microscopes,due to the small de Broglie wavelength of the electrons, enabling the instrumentto resolve fine details as small as single atoms. TEM images are due to the phe-nomenon of absorption of electrons in the material which is in turn related to thethickness and composition of the material.

Infrared Reflection Absorption Spectroscopy (IRRAS)

Infra red beam can be resolved into polarized components in which the electric vec-tor oscillation is parallel and perpendicular to the plane of incidence, respectively.When one polarized component hits a metal surface, a stationary wave is generated,resulting from the interference between incident and reflected beams. The spectralband features in IRRAS mode, peak positions, band shapes and intensities will con-siderably differ from the transmission spectra of the material. In IRRAS spectra, ifthe film thickness is thin enough in comparison to the wavelength of the incident IRlight, the normalized reflectivity change increases in proportion to the film thicknessd (up to nanometer dimension) and quantitative information on the thickness can beobtained [8].

Micro Raman (μRAMAN)

The new generation of Raman microscopy offers a powerful non-destructive andnon-contact method of sample analysis. In general, Raman technique enables thestudy of selected vibrations in molecules and solids through the interaction of light[9, 10]. It relies on inelastic scattering of monochromatic light, in visible, nearinfrared and near ultraviolet spectral regions. Micro-Raman spectroscopy allowsthe study of small sample regions down to the micron scale The spatial distributionof the Raman intensity can be studied giving a 2D map of the sample and depthprofiles [11].

Surface Enhanced Raman Spectroscopy (SERS)

The surface enhanced Raman spectroscopy is a surface sensitive technique witha greatly enhanced signal by molecules adsorbed on rough metal surfaces; theenhancement factor can be as much as 1014–1015, which permits this techniqueto be sensitive enough to detect single molecules. In most experiments the SERS

264 Appendix:Principal Characterization Techniques of Nanostructured Macromolecules

spectra are very similar to the non-surface enhanced spectra, but often differencesin the number of detected modes present can be observed. When molecules areadsorbed to a surface, the symmetry of the system can change, slightly modifyingthe symmetry of the molecule, which can lead to differences in mode selection. Thistechnique results selective for the study of adsorption on surfaces and of the orien-tation in which the molecule is attached, with resolving power up to monolayers[12].

Dynamic Light Scattering (DLS)

Dynamic light scattering is a non-invasive, well-established technique used for mea-suring the size of molecules and particles typically in the submicron region and,with the latest technology, for the investigation of sizes smaller than 1 nm. Whenthe light hits nanoparticles, it scatters in all directions (Rayleigh scattering); if thelight source is a laser a time-dependent fluctuation in the scattering intensity can beobserved, due to the Brownian motion in solution. The dynamic information of theparticles can be used to determine the size distribution profile of small particles insolution [13]. The diameter measured by DLS is called the hydrodynamic diameterand refers to how a particle diffuses within a fluid.

References

Books and Web Sites

1. West P, Introduction to atomic force microscopy: theory, practice and applications – www.AFMUniversity.org

2. Morris VJ, Kirby AR, Gunning AP (1999) Atomic force microscopy for biologists. ImperialCollege Press, London

3. Goldstein GI, Newbury DE, Echlin P, Joy DC, Fiori C, Lifshin E (1981) Scanning electronmicroscopy and x-ray microanalysis. Plenum Press, New York

4. Hecht B, Sick B, Wild UP, Deckert V, Zenobi R, Martin OJF, Dieter DW (2000) Scanningnear-field optical microscopy with aperture probes: fundamentals and application. J ChemPhys 18:112

5. Kaupp G (2006) Atomic force microscopy, scanning nearfield optical microscopy andnanoscratching: application to rough and natural surfaces. Springer, Heidelberg

6. Bonnell DA, Huey BD (2001) In: Bonnell DA (ed) Scanning probe microscopy andspectroscopy: theory, techniques, and applications, 2nd edn. Wiley-VCH, Inc, New York

7. Egerton R (2005) Physical principles of electron microscopy. Springer, Heidelberg8. Trenary M (2000) Ann Rev Phys Chem 51:381–4039. Gardiner DJ (1989) Practical Raman spectroscopy. Springer Verlag, Berlin

10. Weber WH, Merlin R (eds) (2000) Raman scattering in materials science, Springer series inmaterials science, vol 42. Springer Verlag, Berlin

11. Baia L, Gigant K, Posset U, Schottner G, Kiefer W, Popp J (2002) Appl Spectrosc 56:409–54812. Nie S, Emory SR (1997) Science 275:1102–110613. Chu B (1992) Laser light scattering: basic principles and practice, 2nd edn. Academic Press,

Elsevier, London

Index

AAFM, see Atomic force microscopy (AFM)Aggregation equilibria, 5AHB, see Angular hole burning (AHB)All-optical modulators, 148

See also DevicesAll-optical poling (AOP)

centrosymmetric bisazomolecule, 136experimental setup for, 135four-level scheme of, 134interference process, 133photomultiplier tube, 135–136trans-cis and cis-trans transitions, 134–135See also Poling techniques

Amino-acid-functionalized gold nanoparticlesand SPNA-derived substrates

chemical structure of, 231Amphiphilic dendrimers, vectors for gene

delivery, 12Amphiphilic graft polyphosphazenes

self-assembly, 8Angular hole burning (AHB), 133–134Anodic aluminum oxide (AAO)

template, FESEM images of, 21AOP, see All-optical poling (AOP)Arachidonic acid (AA)

in situ o and o-1 hydroxylation of, 237Atmospheric plasma (AP) study, 30–31Atomic force microscopy (AFM), 26–27

Hook’s law, 261operation, modes, 261–262

Atom transfer radical polymerization (ATRP),8, 28, 33

mechanism for, 34methods for conducting, 35reverse, drawback of, 35simultaneous normal and reverse initiation

(SR&NI) ATRP, 36TEM micrographs after, 34

4-ATP-CoTBPPf-Py-C60 system, 181–182ATR-FTIR spectroscopy, see Attenuated

total reflection–Fourier transforminfrared spectroscopy (ATR-FTIRspectroscopy)

ATRP, see Atom transfer radical polymeriza-tion (ATRP)

Attenuated total reflection–Fourier transforminfrared spectroscopy (ATR-FTIRspectroscopy), 26–27

Auger electrons, 168, 170, 172Avastin R©, see BevacizumabAzobenzenesulfonic acid, amphiphilic micelle,

22

BBacillus sphaericus NCTC 9602, NEXAFS

spectra, 187Bevacizumab, 243Bifunctional linkers, 222Biomolecule-functionalized nanoparticles for

controlled chemical reactivitycatalysts

fuel processing, 226–227and heterogeneous catalysts, use, 227nanoparticles and vaccines delivery

GI tract, 238PLGA/PLGA–PEG and PCL–PEG, 239RGD ligand, 239

protein adsorption on solid surfaces, 227chitosan (D-glucosamine), 235CRL bioconjugates, 230–231FTIR and CD spectroscopy, 232geo-inspired synthetic chrysotile, 232HCAII, 228–229immobilized lipase, kinetic parameter

Km values, 235–236interfacing with CNTs, 229–230

265

266 Index

lysozyme adsorption on silica particles,233

NMR spectroscopy used, 228PANCMA fibrous membranes, 236protein’s secondary structure, effect of

particle curvatures on, 229R-chymotrypsin (ChT), 231–232support and enzyme immobilization,

preparation, 235SWCNTs, oxidation of, 229–230

whole cells, immobilizationdamaged tissues, repair/replacement,

236gold NPs, 238ı-CP and SAMs, 237magnetic NPs in dextran matrix, 238NADPH, 237–238organic fluorophores, 238photosensitizer, 238Yarrowia lipolitica and Candida

bombicola, 237Biomolecule-functionalized nanoparticles

synthesiselectrostatic adsorption, functionalization,

220NPs, with immunoglobulin G (IgG)

molecules, 221streptavidin/biotin/(EG3-S-)/GSH,

interaction with, 221and microbial systems

bacteria, use of, 223flavin recognition by diaminopyridine

functionalized Au NPs, 224intrinsic properties, 224–225

specific affinity interactions, 222T4-5X-Amdex-CdS conjugate and its

binding, 223thiol derivatives, chemisorption

anchor groups, 222Biomolecule-nanoparticle interface properties

biomacromolecules, surface recognitionchallenges for, 225

MPCs and MMPCs, 226Bionanofabrication process, 64Biosensors based on nanomaterials, 67Biphasic electropolymerization, 46Block copolymers self-assembly, 8–9

2-(4′-hydroxybenzeneato) benzoicacid, 10

labyrinth-like patterns of, 10moire-type superstructures, 10polystyrene-block-poly (4-vinylpiridine),

10

Bottom-up approaches, 2Bragg equation, 192Bremsstrahlung continuum, 192Brillouin scattering, 90Building block approach, for spectral

assignment, 173–174

CCandida rugosa lipase (CRL), 230, 233Carbon nanotubes (CNTs)

biological applications, 244use, 244–245

Cationic linear poly(ethyleneimine) layer-bylayer assembly, 6

Cetuximab, 243Cetyltrimethylammonium bromide (CTAB),

20Chitosan (D-glucosamine), 3, 235R-Chymotrypsin (ChT), 233

molecular structure of, 231monolayer-controlled diffusion of, 231

CNTs, see Carbon nanotubes (CNTs)Coarse-grained lattice gas model, 6Coaxial electrospinning, 64Cobalt tetra-butyl-phenyl porphyrins

(CoTBPPf), 181–182Colloidal nanolithography, 24Comb-shaped supramolecules self-assembly, 8Conductive polymer nanotubes, controlled

electrochemical synthesis, 47π-Conjugated polymers self-assembly

polyacetylenes and polyynes, 17–18polyaniline (PANI), 13–15polypyrrole (PPy), 15polythiophene (PTh), 16–17

Contact poling, 131–133air and voltages, 132bleaching effect, 132configuration for, 131coplanar electrodes, 131EO core material, 132MZ modulators, 132See also Poling techniques

Controlled-living radical polymerization(CRP) methods, 33

Coplanar waveguide (CPW) structure, 132Core level chemical shift, 195–196Corona poling, 129–131

effect of atmosphere on, 130growth and decay of polar order in, 130set-up for, 129swelling–poling–deswelling procedure,

131

Index 267

thermal-or photo-cross-linking, 130See also Poling techniques

CRL, see Candida rugosa lipase (CRL)CRP, see Controlled-living radical polymeriza-

tion (CRP) methodsCTAB, see Cetyltrimethylammonium bromide

(CTAB)CuPc/SAM/Au systems, 180Cyclodextrin (CyD), 33

DDBSA, see Dodecil-benzenic sulphonic acid

(DBSA) dopantDeep silicon etching, 24Dendrimers

macroinitiators, 8networks and NEXAFS, 190self-assembly, 11

applications in neurodegenerativediseases, 13

box-nanocrystals, 12CdSe dendron stabilized nanoclusters,

12chain entanglement of linear polymers,

13gold cluster superstructures, 13liquid crystalline materials, 13L-lysine building-blocks, 12metal coordination chemistry and, 12nanoclusters and nanotubes, 12PAMAM-DNA complex, 12

Devicesall-optical modulators, 148birefringence effect, 151Bragg grating filter, 155channel waveguide of EO polymer with

Bragg grating, 157charge-transfer bridge, 158distributed Bragg reflector (DBR), 156electro-optic

and all-optical switches, 150–151modulators, 149switches, 152

fabrication techniqueschannel waveguides, 138direct patterning, 140–142lateral confinement, 138photolithography, 139–140representation of, 138–139soft lithography, 142–144

Fabry-Perot etalon devices, 156high-Q polymer microring resonators, 154light modulators

microring resonator modulator,149–150

ring and straight waveguide, 149Mach-Zehnder waveguide modulator,

145–148microring wavelength filters, 155molecular switch, 154organic NLO materials for, 146photonic switching, 151properties of, 147reflective-type resonant grating waveguide

modulator, 144surface-relief gratings, 155tuneable wavelength filter, 157ultra-fast optical switches, 153–154

Dextran, 3DFT, see Fluids density functional theory

(DFT)Diblock copolymer

amphiphilic LC-coil, TEM micrographs of,34

drying-mediated self-assembly, 6Diffusion processes, 6Dimethylaminoindoaniline (DIA), 93Direct laser interference micro-nanopatterning

(DLIP), 24Direct patterning processes, 140–142Dissipative particle dynamics (DPD) method,

10DLIP, see Direct laser interference

micro-nanopatterning (DLIP)DLS, see Dynamic light scattering (DLS)Dodecil-benzenic sulphonic acid (DBSA)

dopant, 15DPD, see Dissipative particle dynamics (DPD)

methodDrug delivery and cancer therapy, nanostruc-

tured materialschemotherapy, 241

(PEG), 242polymeric NPs, 242

and magnetic NPs, 245advantages, 247–248development of, 246–248EPR, 246FluidMAG R©, 247HRTEM images, 247MagNaGel R©, 247

microfluidics, 243CNTs, 244–245

nanoparticles and gene deliverycomposite multifunctional nanoparti-

cles, role, 242–243

268 Index

LBL method, 242PNIPAM and PEG, 242

targeting moleculesmonoclonal antibodies (mAb), 243SELEX and FRs, 243

Drying kinetics, 6Drying-mediated self-assembly, 6Dynamic light scattering (DLS), 261, 264

EEDOT, see 3,4-Ethylenedioxythiophene

(EDOT)E-DPN, see Electrochemical dip-pen

nanolithography (E-DPN)EFISH, see Electric field induced second

harmonic (EFISH) techniqueEF-TEM, see Energy filtered-transmission

electron microscopy (EF-TEM)Electric field induced second harmonic

(EFISH) technique, 89Electroauxiliary (EA), 38Electrochemical dip-pen nanolithography

(E-DPN), 24Electrochemical methods, 3

aligned nanostructures, 45–46coaxial nanowires and nanotubes, 46–48electron-transfer process, 38electrosynthesis, 38features, 36nanowires and nanotubes, 42–45reaction media, role of, 40–42

Electrochemical template method, 42Electro-optical absorption (EOA) spectroscopy,

90Electro-optic modulators (EOM), 119, 149

See also DevicesElectrospinning technology, 2–3

coaxial, core-shell nanofibers andnanotubes, 64–65

electrospun fiber properties, 65fibers produced by, 57overview, 55parameters affecting, 58

applied voltage, 59capillary tip and collector, distance

between, 60choice of solvent, 60–61nozzle configuration, 62–63polymer concentration, 61polymeric fibers, 60solution conductivity, 61–62

process and mechanism, 57–58representation of, 56

Electrospun nanofiber matrices, 249Electrospun poly(vinyl alcohol) nanofibers,

64Electrosynthesis, 37Emulsion polymerization, 2–3

critical parameters for, 53–54features, 48–50kinetics process in, 50theoretical overview

interval I, 50interval II and III, 51rate of polymerization, 52

Energy filtered-transmission electronmicroscopy (EF-TEM), 230

Enhanced permeation and retention (EPR),246

EOM, see Electro-optic modulators (EOM)EPR, see Enhanced permeation and retention

(EPR)Erbitux R© , see CetuximabETFE, see Poly(ethylene-alt-

tetrafluorethylene) (ETFE)3,4-Ethylenedioxythiophene (EDOT), 16Evaporation procedures, 6

FFabry-Perot etalon devices, 156Ferromagnetic Co nanoparticles self-assembly,

6Flash welding, 67FluidMAG R©, 247Fluids density functional theory (DFT), 5Folate receptors (FRs), 243Folded accordion polymers, 107Fourier transform infrared spectroscopy

(FTIR), 232Four wave mixing geometry, 133Free-radical graft polymerization, 29FRs, see Folate receptors (FRs)FTIR, see Fourier transform infrared

spectroscopy (FTIR)Fullerenes and ZnPf, molecular arrangement

of, 182–183

GGas-phase silylation, 29Gastrointestinal (GI) tract, 238Gel-phase assemblies of dendritic molecules,

11Glycidyl methacrylate (GMA), 33Glycine adsorption, study by XPS, 206GMA, see Glycidyl methacrylate (GMA)Gold cluster superstructures, 13

See also Dendrimers

Index 269

Graft polymerization, 2atom transfer radical polymerization,

33–36characterization, 26features of, 25–28free radicals, 28–30plasma surface treatment and plasma-

induced graft polymerization,30–33

and polymer grafting, 25

HHCAEC, see Human coronary artery

endothelial cell (HCAEC)HCAII, see Human carbonic anhydrase II

(HCAII)HER2, see Human epidermal growth factor

receptor 2 (HER2)Herceptin R© , see TrastuzumabHierarchical self-assembly approach, 7–8Highest occupied molecular orbital (HOMO)

of monomer, 38Highly ordered pyrolytic graphite (HOPG)

electrode, 39High-Q polymer microring resonators, 154

See also DevicesHigh resolution transmission electron

microscopy (HRTEM)images, 247

Homogeneous electrolysis processes, effect ofultrasounds on, 39

Host-guest systems, 9HRTEM, see High resolution transmission

electron microscopy (HRTEM)Human carbonic anhydrase II (HCAII), 228Human coronary artery endothelial cell

(HCAEC), 251Human epidermal growth factor receptor 2

(HER2), 240Human serum albumine (HAS), 185–186Hyaluronic acid derivatives, 3Hybrid (Au-PPy-Au) nanowire arrays, 20Hybrid systems, 3Hydrodynamic effects, 6Hydrophobic drug, 7Hyper-Rayleigh scattering (HRS), 90

IInfrared reflection absorption spectroscopy

(IRRAS), 261, 263Ionic liquids, chemical structures of cations

and anions, 40IRRAS, see Infrared reflection absorption

spectroscopy (IRRAS)

Isocyanate end-capped prepolimer, 110Isothermal decay method, 137

JJoint experimental-theoretical approach, 7

KKleinman symmetry, 82Kolbe electrolysis, 39

LLamellae-within-cylinders structure, 8Langmuir-Blodgett technique, 2, 21Laser micro/nanopatterning, 2Layer-by-layer (LBL) method, 6, 242Layered double hydroxides (LDHs), 220LDHs, see Layered double hydroxides (LDHs)Light modulators

microring resonator modulator, 149–150ring and straight waveguide, 149See also Devices

Lipid tubules, 22Liquid crystalline assemblies of dendritic

molecules, 11Liquid-phase silylation, 29Lithium Niobate (LiNbO3), 119

devices, growth and patterning, 120Living radical polymerization, 33Lotus effect in macromolecules, 66

MmAb, see Monoclonal antibodies (mAb)Mach-Zehnder waveguide modulator, 145–148

interferometer, 119–120See also Devices

MagNaGel R©, 247Mass-transport process, 39MBE, see Molecular beam epitaxy (MBE)Metal clusters, 200–201Metal ion coordination polymers self-assembly,

10Metalloporphyrins, 178, 181–182

and synthesis of supramolecular systems,181

Metal organic chemical vapour deposition(MOCVD), 120

Microcontact printing (ı-CP), 237Microphase separation, 24Micro Raman (μRAMAN), 261, 263Microscopy techniques, 26–27Mixed MPCs (MMPCs), 226MOCVD, see Metal organic chemical vapour

deposition (MOCVD)Molecular beam epitaxy (MBE), 120

270 Index

Molecular imaging, nanomaterials applicationsin

fluorophores, 239human epidermal growth factor receptor 2

(HER2), 240nanomaterials, superior properties,

239–240QD, 240

Molecular layer deposition (MLD) process,199

Molecular self-assembly, 4Molecular template-assisted electrosynthesis,

45Monoclonal antibodies (mAb), 243Monolayer-protected clusters (MPCs),

226Monte Carlo simulation techniques, 6MPCs, see Monolayer-protected clusters

(MPCs)μRAMAN, see Micro Raman (μRAMAN)Multi walled carbon nanotubes (MWCNTs),

244MWCNTs, see Multi walled carbon nanotubes

(MWCNTs)

NNa-DNA/POMA-ES system, 14NADPH, see Nicotinamide adenine

dinucleotide phosphate (NADPH)Nanobiotechnology, 219

bio-nanohybrid materials, science, 220nano-HA, see Nano-hydroxyapatite (nano-HA)Nano-hydroxyapatite (nano-HA), 250Nanoimprint lithography (NIL), 142–144Nanomolding, 24Nanoparticles (NPs), 222–239

with immunoglobulin G (IgG) molecules,221

Nanostructured macromoleculesapplications and perspectives, 65–69self-assembly

aggregation, 4block copolymers, 8–102D and 3D structures, 4dendrimers, 11–12drying-mediated, 6evaporation procedures and, 6features, 4hierarchical based on LbL, 6–8hollow hydrophilic metal functionalized

nanostructures, 9porphyrins, 8spheres and wire-like threads, 8

theoretical approach, 5top-down and bottom-up approach, 5

systemsand NEXAFS, 174–178use of, 166XPS, investigations by, 199–200

Near edge X-ray absorption fine structurespectroscopy (NEXAFS), 165–166

apparatus for, 172application to molecular systems

biomolecular, 183–187nanostructured, 174–178NLO molecules, 188–190organometallic macromolecules,

178–183principles of

angular dependent measurements,170–172

selection rules, 169–170spectral features, 167–168surface sensitivity of, 168–169

resonances, 167–168spectral assignment, method for, 173–174

Near-field optical microscopy (NOM),261–262

NEXAFS, see Near Edge X-ray AbsorptionFine Structure spectroscopy(NEXAFS)

Nicotinamide adenine dinucleotide phosphate(NADPH), 237–238

Ni phtalocyanine, 178–180NLO, see Nonlinear optics (NLO)NLO macromolecular systems

and device fabrication techniques, 138–139direct patterning, 140–142photolithography, 139–140soft lithography, 142–143

devices based onfilters, 154–157microring resonators, 154modulators, 144–150other applications and devices, 158sensors for electric field, 158switches, 150–154

optical characterization of, 121–123nonlinear ellipsometry, 126–128second harmonic generation, 124–126

orientation stability, 136–138poling techniques, 128–129

all-optical poling technique, 133–136contact poling, 131–133corona poling, 129–131

Index 271

N-Methyl-2-pyrrolidone (NMP), graftpolymerization in, 26–27, 181

NOM, see Near-field optical microscopy(NOM)

Non centrosymmetric crystals, 119Nonlinear ellipsometry

single wavelength reflection configuration,126

Nonlinear optical (NLO) properties of organicmaterials, 119

See also NLO macromolecular systemsNonlinear optics (NLO), 79, 84

chromophores, 922 D, 94DIA, limiting resonance formulae for,

93forming acentric crystals, 96molecular nonlinearity of, 93zwitterionic, limiting resonance forms

for, 94molecules, 188–190, 208–211polymers, 98

electric poling for, 99SHG NLO data, 99–100

Nonporous alumina templates, 7NPs, see Nanoparticels (NPs)

OOctadecylamine (ODA)

Candida bombicola, aqueous dispersion,237

OLEDs/PLEDs, see Organic/polymer light-emitting diodes (OLEDs/PLEDs)

Oligo(phenyleneethynylene) (OPE), 200Optical characterization, 121

birefringence of systems, 123extraordinary index, 123induced electric dipole, 123isotropic distribution of molecular

orientation, 123linear contribution, 122macroscopic linear polarization, 123microscopic hyperpolarizability,

relationship between, 122molecular and laboratory axes, 122molecule-based coordinate system,

122–123polarizability tensor, 122quasi-one-dimensional molecules, 122refractive index, 123

Optical nonlinearity in materialsderivatives, 81electric dipole moment and Taylor series,

81–82

electro-optic coefficients, 85experimental techniques, 89–91Kleinman symmetry, 82material property and external perturbation

tensor, 80–81molecular optical nonlinearities, 85

dipole moment operator, 88explicit form of components, 86Gaussian units, 87HOMO-LUMO transition, 88–89intrinsic permutation and, 86polarizability and hyperpolarizability

tensors, 86reference system, 87second order perturbation theory, 87two-level model, 88

optimizing, 91–95Pockels effect, 84–85pump-waves

of frequency, 82–83SHG process, 84

susceptibility tensor, 84two-index and three-index in SHG

coefficients, 84Organic materials, requirements for

commercial use of, 121See also NLO macromolecular systems

Organic optoelectronics, in communicationtechnology, 120

Organic/polymer light-emitting diodes(OLEDs/PLEDs), 16

Organometallic macromolecules, andNEXAFS spectroscopy, 178–183

Orientation stabilityactivation energy of, 137double exponential function, 137first decay component, 137polymer glass transition temperature,

136–137second order NLO activity decay time,

136–137SHG intensity, 137Smoluchowski equation, 136time evolution, 136

Oriented gas model, 122Osmosis, 2Oxidative polymerization, 15

PPANANA, see Poly(aniline-co-anthranilic

acid) (PANANA)PANI, see Polyaniline (PANI)PCL, see Pseudomonas cepacia lipase (PCL)

272 Index

PCL–PEG, see Poly(ε-caprolactonecoethyleneglycol) (PCL–PEG)

PDDA, see Poly(diallyldimethylammoniumchloride) (PDDA)

PDMS, see Poly(dimethylsiloxane) (PDMS)stamps

PDPSA, see 3-Pentadecyl phenol-4-sulphonicacid (PDPSA)

PEDOT, see Poly(3,4-ethylenedioxythiophene)(PEDOT)

PEG, see Polyethylene glycol (PEG)3-Pentadecyl phenol-4-sulphonic acid

(PDPSA), 22pGMA, see Poly(glycidyl methacrylate)

(pGMA)Photo-assisted poling (PAP), 128–129Photolithography, 139–140Phthalocyanines, 179PIGP, see Plasma-induced graft polymerization

(PIGP)Plasma-induced graft polymerization (PIGP),

28, 30–31multistep process of, 32

Plasma surface treatment, 30–33Plasmid DNAcopolymers (dendritic poly

L-lysine and linear PEG blocks)self-assembly, 12

PLGA, see Poly(lactide-co-glycolide) (PLGA)PLLA-CL, see Poly(L-lactic acid)-co-poly(e-

caprolactone) (PLLA-CL)PMMA, see Polymethylmethacrylate (PMMA)PNIPAM, see Poly(N-isopropylacrylamide)

PNIPAMPockels effect, 84–85Poling techniques, 128

all-optical polingcentrosymmetric bisazomolecule, 136experimental setup for, 135four-level scheme of, 134interference process, 133photomultiplier tube, 135–136trans-cis and cis-trans transitions,

134–135contact poling

air and voltages, 132bleaching effect, 132configuration for, 131coplanar electrodes, 131EO core material, 132MZ modulators, 132

corona polingeffect of atmosphere on, 130growth and decay of polar order in, 130

set-up for, 129swelling–poling–deswelling procedure,

131thermal-or photo-cross-linking, 130

Polyacetylenes and polyynes, 17–18See also π-Conjugated polymers

self-assemblyPolyamidoamine (PAMAM) dendrimers and

DNA transport, 12Poly(aniline-co-anthranilic acid) (PANANA),

14Polyaniline (PANI), 13

arrays, 14DLIP by, 24

nanowires-gold nanoparticles hybridnetworks, 44

oriented nanowires, 45self assembly

copolymers, 14dispersion polymerization in PVA

matrix and formation, 14emeraldine base (EB) and salt (ES)

forms of POMA, 14morphology of, 23PANI/acid concentration ratio, 14solid state properties of, 22synthesis of, 22tetrachloroaurate use, 14

See also π-Conjugated polymersself-assembly

Polydiacetylene (PDA) films and nanotubes,self assembly, 7

Poly(diallyldimethylammonium chloride)(PDDA), 22

Poly(dimethylsiloxane) (PDMS) stamps, 30Poly(ε-caprolactonecoethylene glycol)

(PCL–PEG), 239Poly(ethylene-alt-tetrafluorethylene) (ETFE),

25Poly(3,4-ethylenedioxythiophene) (PEDOT),

16electrochromic devices based on, 68electrodeposition, 47growth mechanism of, 47oxidative chemical polymerizations of, 20

Polyethylene glycol (PEG), 242Polyferrocenylsilane cores and polyisoprene

coronas self-assembly, 9–10Poly(glycidyl methacrylate) (pGMA), 25Poly(lactide-co-glycolide) (PLGA), 239, 250Poly(L-lactic acid)-co-poly(e-caprolactone)

(PLLA-CL), 251Polymer grafting, 2

Index 273

Polymeric NPs, 242Polymethylmethacrylate (PMMA), 3, 230Polymethylmethacrylate (PMMA) diblock

copolymers (PS-b-PMMA), 10Poly(N-isopropylacrylamide) PNIPAM, 242Poly(N-methylpyrrole) (PNMPy), oxidative

chemical polymerizations, 20Poly(N,N-dimethylpropargylamine)

derivatives, 3Poly(o-methoxyaniline) (POMA), 14Polyphenylacetylene (PPA), 17Polypyrrole (PPy) self assembly

aligned PPy by CV electropolymerizations,46

dopant, 15by FeCl3 induced oxidative polymerization,

15films SEM images, 41inverse opal patterns, 23morphology of, 23nanowire arrays, 20oriented nanofibers, 45oxidative chemical polymerizations of, 20TEM images of, 15templated chemical polymerization of, 21template oxidative polymerization of, 23tubules of, 45–46two-step method of preparing nanowires,

44See also π-Conjugated polymers

self-assemblyPoly(sodium-4-styrenesulfonate) (PSS), 22Polystyrene/poly(methyl methacrilate)

(PS/PMMA), 185–186Polystyrene (PS), 10

nanospheres, 44nanostructured as carriers for, 230and polyphenylacetylene, 3templating particles, 22

Polythiophene (PTh), 16–17oxidative chemical polymerizations of, 20See also π-Conjugated polymers

self-assemblyPOMA, see Poly(o-methoxyaniline) (POMA)Porphyrin molecules

arrays, 7self-assembly, 8

Post-bake procedure, 139–140PPA, see Polyphenylacetylene (PPA)Prussian Blue nanoparticles layer-by layer

assembly, 6–7Pseudomonas cepacia lipase (PCL), 230, 233

PSS, see Poly(sodium-4-styrenesulfonate)(PSS)

Pt-polymetallayne, 36-(5-Pyridin-2,yl-pyrazin-2-yl)pyridine-3-thiol

(PPPT), 175, 177

RRAFT, see Reversible addition-fragmentation

chain transfer (RAFT) techniqueReflective-type resonant grating waveguide

modulator, 144See also Devices

Regioregular polyester, 108Reprecipitation method, 8Resonances, in K-shell spectra, 167–168,

173–174Reversible addition-fragmentation chain

transfer (RAFT) technique, 25,52–53

Ribonuclease structure, by NEXAFS spectra,184

Ring opening polymerization (ROP), 8Rituxan R©, see RituximabRituximab, 243Rod-like polymers self-assembly, 8ROP, see Ring opening polymerization (ROP)Rotaxane/dibenzo-24-crown-8 macrocycle, 12

SSAMs, see Self-assembled monolayers

(SAMs)SBP, see Soybean peroxidase (SBP)Scanning electron microscopy (SEM), 26–27,

261back-scattered electrons, 262

Scanning transmission X-ray microscopy(STXM), 184

Scanning tunneling microscopy (STM), 261quantum tunneling, concept, 262

Scienta analyzer, 193, 212Second-harmonic generation (SHG), 83

coefficient and nonlinear susceptibility, 124coherence length, 126Kleinmann’s symmetry condition, 124measurement for poled materials, 125microscopic and macroscopic properties,

124–125nonlinear polarization term for, 124tensors, 124

Second order nonlinear optically activematerials

autoassembling systems, 97chemical strategies, 96

274 Index

cross-linked systems and organic molecularglasses, 109

depoling behaviour, 111multi-component systems, 110one-component cross-linkable systems,

110guest-host systems, 100

electro-optic activity of polymers, 101main-chain NLO polymers

class of, 106folded accordion polymers, 107polyurethane PUY3, 108regioregular P-type, 108transverse (T-type)/parallel (P-type),

106T-type polyurethane based on Y-shaped

chromophore, 107NLO dendrimers, 112–113NLO polymers, 98

electric poling for, 99poling apparatus, 99pseudo-centrosymmetric antiparallel

orientation, 95self-assembled multilayers, construction

of, 97side chain NLO polymer, 101

chromophores of, 102, 104Diels-Alder reaction, 104Knoevenagel condensation, 103Mitsunobu condensation, 103one step synthesis of, 104polyurethane (type II) from

diol chromophore and 2,4-tolylendiisocianate, synthesis of,105

post-functionalization by azo coupling,103

synthetic procedure for, 102time stability and, 103type I, 103

SELEX, see Systemic evolution of ligands byexponential enrichment (SELEX)

Self-assembled ferromagnetic PSCoNPs(DPS-CoNPs) TEM images, 7

Self-assembled monolayers (SAMs), 174–176,237

Self-assembly procedure, 2SEM, see Scanning electron microscopy

(SEM)Semibatch/continuous reaction systems, 49SERS, see Surface enhanced Raman

spectroscopy (SERS)SFG, see Sum-frequency generation (SFG)

Shake-off and shake-up, in XPS, 196SHG, see Second-harmonic generation (SHG)Simultaneous normal and reverse initiation

(SR&NI) ATRP, 36Single-walled carbon nanotubes (SWNTs),

233Smoluchowski model, 136Solar cells, 181, 203Soybean peroxidase (SBP), 233–234Spectator electrons, 196Static-exchange approximation (STEX), for

amino acids, 184–185Step and flash imprint lithography, 144Stilbazolium multilayers, construction of

self-assembled, 210STM, see Scanning tunneling microscopy

(STM)Structure-property relationship of conjugated

nanostructures, 7Sum-frequency generation (SFG), 83Supramolecular self-assembly approach, 7Surface enhanced Raman spectroscopy

(SERS), 261, 263–264SWCNTs, see Single-walled carbon nanotubes

(SWNTs)Synchrotron radiation, 166

for NEXAFS measurements, 170–172Synchrotron radiation-based photoelectron

spectroscopy, 203Synthetic polymers, SEM images of

morphologies, 3Systemic evolution of ligands by exponential

enrichment (SELEX), 243

TTaylor cone, 59–63TEM, see Transmission electron microscopy

(TEM)Template

assisted electropolymerization, 44endo and exotemplates, 19features of, 18nanopatterning of polymers, 23–24polymeric, 20“soap-bubble” use of, 20surfactant, morphologically controlled

nanostructures, 23technique

electrochemical methods, 18grafting polymerization, 18materials in, 22–23

templated assembly of dendrons, 11“templateless” synthesis, 45

Index 275

Teng and Man Technique (TMT), 126electro-optic coefficient, 127experimental set-up, 127–128polymer film between electrodes, 127

Terphenyl-4-thiol (TPT), 175, 177Tethered polymer phases, 2Thiolate β-cyclodextrin self-assembled

monolayers, 45Thiol derivatives chemisorption

covalent binding through bifunctionallinkers, 222

Thiophenes, electropolymerization in,37–38

Tissue engineering, 248electrospinning, 249electrospun nanofiber matrices, 249electrospun nanofibers scaffold

fabrication techniques, 249nanocomposite scaffolds, SEM

micrographs, 250PLGA and nano-HA, 250PLLA-CL and HCAEC, 251pore size distribution, 252use, 249–250

Top-down approaches, 2Total electron yield (TEY) detection, 173Transmission electron microscopy (TEM),

26–27, 261, 263Trastuzumab, 243Triethanolamine, 110Tri-L-(glutamic diethyl esther)-1,3,5-

benzenetricarboxamidesupramolecular assembly,21

UUntemplated assembly of dendrons, 11UV nanoimprint lithography, 143UV-switch able framework, 12

VVapor-phase plasma polymerization, 301-Vinyl-2-pyrrolidone (VP) graft polymeriza-

tion, 32

WWavelength division multiplexers (WDM),

150–151Wet etching process, 141

See also Devices

XX-ray photoelectron spectroscopy (XPS), 165

applications to molecular systemsbiomolecular systems, 205–208nanostructured systems, 198–201NLO molecules, 208–211organometallic macromolecules,

201–205principles of, 190–198

electronic structure and chemical state,195–197

experimental methods, 192–193surface sensitivity, 197–198X-ray photoelectron spectrum, 193–195

X-ray photoemission electron microscopy(X-PEEM), 186

ZZn diethinyl porphyrin (ZnPf), 178